Dithiocarbamate ester bactericides and fungicides

ABSTRACT

The invention is compounds of the formula:   WHEREIN R1 and R2 are each lower alkyl C1-C4 ; R5 is hydrogen or lower alkyl C1-C4 ; and Z is phenyl, 1-naphthyl or substituted phenyl and a method for preparing dithiocarbamate esters. The compounds are useful as bactericidal and fungicidal agents.

Ilnited States Patent [191 Lies et a1.

[ DITHIOCARBAMATE ESTER BACTERICIDES AND FUNGICIDES [75] Inventors: Thomas Andrew Lies, Montgomery Township; James Wellington Clapp, Princeton, both of NJ.

[73] Assignee: American Cyanamid Company,

Stamford, Conn.

[22] Filed: Mar. 24, 1971 [21] Appl.No.: 127,825

[52] US. Cl ..260/455 A, 260/293.68, 260/293.85, 260/306.7, 260/326.83, 260/332.2 R, 260/340.5, 260/347.2, 424/267, 424/270,

FOREIGN PATENTS OR APPLICATIONS 541,048 11/1941 Great Britain ..260/455 A Mar. 27, 1973 OTHER PUBLICATIONS Matsushima et a1. Ovicidal Effects of Aromatic Esters, etc., (1966) CA 67 No. 435340 (1967).

Primary Examiner-Lewis Gotts Assistant Examiner-G. Hollrah Attorney-Robert P. Raymond [57] ABSTRACT The invention is compounds of the formula:

wherein R and R are each lower alkyl C C, R is hydrogen or lower alkyl C C, and Z is phenyl, 1- naphthyl or substituted phenyl and a method for preparing dithiocarbamate esters. The compounds are useful as bactericidal and fungicidal agents.

6 Claims, N0 Drawings DITHIOCARBAMATE ESTER BACTERICIDES AND FUNGICIDES In one respect, the present invention relates to novel I II where Q is a member selected from the group consisting of:

Q is a member selected from the group consisting of:

R and R are loweralkyls of from C,C,,, or when R, and R are taken together with N form a piperidine or pyrrolidine nucleus;

R is a loweralkyl of from C -C R is hydrogen, phenyl or substituted phenyl;

R is hydrogen or loweralkyl of from C C X is acetyl or benzoyl;

and

RsCHNOz l-naphthyl, 2-furyl, Z-thienyl, 5-chloro-2-thienyl, and substituted phenyl including 3,4-methylenedi0xyphenyl, 4-methoxy, 4-bromo, 3,4-dichloro, 2-chloro, 4- isopropyl, 2-acetoxy-3-methoxy, acetoxy and 2-chloro-5-nitrophenyl.

The present invention also relates to the use of the above-identified dithiocarbamate esters as antibacterial and antifungal agents effective for protecting living plants from attack by such pathogenic organisms. The invention further relates to processes for the processes for the preparation of these new dithiocarbamate esters.

In accordance with the invention, Type 1 compounds having the structure:

can be prepared by reacting an appropriately substituted dialkylammonium dialkyldithiocarbamate with formaldehyde in the presence of nitromethane. However, when benzaldehyde is employed in this reaction, the a-(nitromethyDbenzyl dimethyldithiocarbamate is formed and treatment of this product with additional dialkylammonium dialkyldithiocarbamate in the presence of formaldehyde yields the phenyl-substituted compound (i.e., Type 7 where Z is phenyl). Similarly, treatment of any of the Type 6 compounds in which R is hydrogen with additional dialkylammonium dialkyldithiocarbamate and formaldehyde in the presence of carbon disulfide yields the Type 7 dialkyldithiocarbamate esters. The reactions are preferably run in the presence of carbon disulfide and at a reaction temperature not exceeding about 50C. Generally, about two mole equivalents of the dialkyldithiocarbamate and two mole equivalents of the aldehyde per mole equivalent of the nitromethane are used.

Graphically, these reactions may be illustrated as follows:

3,4-dimethoxy, 4-

Compounds of Type (2) having the structure:

R NO:

Type 3 compounds are readily prepared by reacting approximately 1 mole equivalent of nitroalkane with 1 mole equivalent of an appropriately substituted dialkylammonium dialkyldithiocarbamate, preferably dissolved in a lower alcohol of from C,C.,, and 2 mole equivalents of an appropriate aldehyde. The reaction is preferably carried out at a temperature below about 50C. and is graphically illustrated as follows:

In the above reaction R R R and R have the meanings set forth above. Where R, is substituted phenyl, there may be one or two substituents included on the ring, and the substituents may be any of the group selected from the halogens (i.e., chloro, fluoro, bromo or iodo), methyl or ethyl, m-nitro, methoxy or ethoxy.

Compounds of Type 4 can be prepared by reacting essentially equimolar amounts of a dialkylammonium dialkyldithiocarbamate with formaldehyde and (1) a phenacyl or acetonyl dialkyldithiocarbamate or (2) 2,4-pentanedione in the presence of carbon disulfide and at a temperature below about 50C. The reaction may be graphically written:

and R R X and Y are as defined above.

Compounds of Type 5 are synthesized by reacting a dialkylammonium dialkyldithiocarbamate with approximately an equimolar amount of rhodanine and formaldehyde with about one-half molar amount of carbon disulfide in a lower alcohol C,-C,. The reaction is generally carried out at a temperature below 50C. The reaction may be illustrated as follows:

wherein R and R are as described above.

Type 6 compounds which have the formula structure:

The required dialkylammonium dialkyldithiocarbamate may be prepared in a separate reaction for use in the above reaction, or for greater process economy, it

may be formed in the reaction mixture by gradual addition of the amine to a solution of the nitrovinyl compound and carbon disulfide.

When the ammonium salt of a dialkyldithiocarbamic acid is employed, an acid such as acetic acid or hydrochloric acid is added as required in portions as the reaction proceeds, so that the concentration of free ammonia is minimized. An excess of acid at any time is Type 6 compounds having the formula structure:

tion proceeds, so that the concentration of free ammonia in the reaction mixture is minimized:

R Rs-CHNO2 Compounds of Type (7) can be prepared by reacting. dithiocarbam ate esters having the formula structures:

R CHzNOz R CHZNOQ with equimolar amounts of formaldehyde and a dialkylammonium dialkyldithiocarbamate in aqueous lower alcohol, C,-C,, or aqueous dimethylformamide solution containing carbon disulfide at a temperature of from 20C .-50C. The reactions may be graphically written:

R GHzNOz Type 1 compounds are exemplified in Examples 1 through 3, Type 2 in Examples 5 and 6, Type 3 in Examples 7 and 8, Type 4 in Examples 9 through 11, Type 5 in Example l2, Type 6 in Examples 13 through 35, and Type 7 in Example 4.

Although some examples show different molar ratios of reactants, the processes are advantageously carried out with the quantities of reactants shown in the generic process equations.

Suitable solvents for the reactions are anhydrous or aqueous, one or more normal or iso-lower aliphatic alcohols, C -C and dimethylformamide.

When the product precipitates from the reaction mixture, it is isolated by filtration. Products soluble in the reaction medium are isolated by diluting the reaction mixture with water and extracting the products from the mixture with ether, methylene chloride or other suitable water-immiscible solvent. Further purification is accomplished by recrystallization or chromatography.

The generic process equations for structures 1, 2, 4 and 6 show that amines are liberated as a by-product of the reactions. It is considered part of the invention that removal of the liberated amine (as by protonation, reaction with carbon disulfide, or other chemical combination) results in higher yields of purer products.

In Example 15, the preparation of a- (nitromethyl)benzyl l-pyrrolidinecarbodithioate from ammonium l-pyrrolidinecarbodithioate, acetic acid was added at the end of the reaction to combine with the liberated ammonia.

in Example 35, the preparation of oz- (nitromethyl)benzyl N-methyldithiocarbanilate, acetic acid was added in portions during the reaction to combine with the liberated ammonia.

In nearly all other examples where an amine is liberated, sufficient carbon disulfide was added to the reaction mixture at the start of the reaction to combine with the amine as it was liberated, to give dithiocarbamate salts as by-products:

Reduction of the free amine concentration prevents undesirable side reactions, some of which are:

(l) R] /R /R;

\N s s mN (112 llN n, n: H:

R 1 li N us s ell? -N IlN R2 R2 R;

For the ti-nitrostyrene reactions:

CH=CHNOz HN R2 4111-o1m10;

(3) Polymerization of the ,B-nitrostyrene. (4) For all products where a \CII NO2 moiety is in the presence of formaldehyde:

n, N0: R1

f N01 who N ("Cll2 N m0 I H R: R:

The compounds of the present invention are useful as antibacterial and antifungal agents and are particularly effective for protecting agronomic crops, both growing and harvested, from attack by pathogenic bacteria and fungi.

As used herein, the term agronomic crops is meant to include (1) field crops SUCH as grains, forage, pasturage, oil and seed crops, fibers, roots and tubers, sugar and specialties such as tobacco and hops, and (2) horticultural crops such as tree fruits and citrus fruits, berries and grapes, nuts, vegetables, herbs, ornamentals, flowers and the like. These compounds may also be used for the protection of leather goods, textiles, and fibers, in the manufacture of paper or pulp and in process water or the like.

In practice, the active compounds are generally prepared as dusts, dust concentrates, wettable powders or the like.

The dusts can be prepared by grinding about 1 percent to 15 percent by weight of the active compound with about 99 percent to percent by weight of an inert diluent such as kaolin, attaclay, walnut shell flour, tale, pumice, diatomaceous earth or the like.

Dust concentrates are made in similar fashion excepting that percent by weight of active ingredient is increased to about 16 percent to 75 percent of the composition.

Wettable powders are prepared in the same manner as dust concentrates, but usually contain, in addition to the active ingredient and solid diluent, from about 1 percent to 5 percent by weight of a wetting agent such as sodium isopropylnaphthalenesulfonate or the sodium salt of a sulfonated naphthalene formaldehyde condensate, and from about 1 percent to 5 percent by weight of a dispersing agent such as hydroxyethylcellulose. A typical formulation would be 50 percent by weight of active ingredient, 2 percent of the dispersing agent, 5 percent of the wetting agent and 43 percent attapulgite.

In using wettable powder, the formulated material is generally dispersed in water and applied as a liquid spray to the crops, textiles, fabrics, paper or the like, which are to be protected from attack by fungi. Usually the sprays applied to crops are used in sufficient quantity to provide about one-eighth pound to about 10 pounds per acre of the active dialkyldithiocarbamate.

The invention is further illustrated by the following examples which are not to be taken as being limitative thereof. In each case, parts and percentages are by weight unless otherwise indicated.

EXAMPLE 1 2-Nitrotrimethylene Dimethyldithiocarbamate and Related Compounds Method A Nitromethane (9.2 grams, 0.15 mole) was added to a solution of dimethylammonium dimethyldithiocarbamate (18.0 grams, 0.108 mole) and formaldehyde (15.0 grams of 37 percent aqueous solution, 0.185 mole) in percent ethanol (50 ml.). The ensuing reaction was first endothermic, and then became exothermic. The reaction temperature was held below 45 with ice-cooling of the vessel. After 1 hour, the

reaction mixture was cooledin ice and the precipitated product was filtered off, washed with water, and dried in air. The crude product melted at 130C.-133C. and weighed 11.9 grams (67 percent yield). Three recrystallizations from hot acetone solution gave pure 2-nitrotrimethylene dimethyldithiocarbamate melting at 133C.-137C. (prior sintering, gas evolution). The

structure was determined by infrared and nuclear magnetic resonance spectra and elemental analysis.

Analysis Calculated for C I-1, N S,O C, 33.01; H, 5.23; N, 12.83; S, 39.16. Found: C, 33.24; H, 5.24; N, 12.86;S,39.15.

Method B.

of the reaction, the reaction mixture was cooled to 5C. and the precipitated product was filtered off, washed with cold methanol and water, and dried in air. The yield of 2-nitrotrimethylene dimethyldithiocarbamate melting at lC.-l35C. (prior sintering, gas evolution) was 750 grams (91 percent).

Following either Method A or B but substituting diisopropylammonium diisopropyldithiocarbamate, ethylmethylammonium ethylmethyldithiocarbamate, or dibutylammonium dibutyldithiocarbamate for dimethylammonium dimethyldithiocarbamate yields the corresponding Z-nitrotrimethylene diisopropyldithiocarbamate, Z-nitrotrimethylene ethylemthyldithiocarbamate, or 2-nitrotrimethylene dibutyldithiocarbamate.

Following either Method A or B- but substituting 95 percent ethanol or Z-propanol for methanol yields 2- nitrotrimethylene dimethyldithiocarbamate.

EXAMPLE 2 2-Nitrotrimethylene Diethyldithiocarbamate Formaldehyde (16.4 grains of arse 15min; solution, 0.2 mole) and nitromethane (9.2 grams, 0.15 mole) were added to a solution of 'diethylammonium diethyldithiocarbamate (22.2 grams, 0.1 mole) and carbon disulfide (7.6 grams, 0.10 mole) in ethanol (175 ml.). The temperature of the resulting reaction was kept below 35C. with a cooling bath. After one hour the product was filtered off, washed with ethanol and ether, and dried in air. The crude product, which weighed 22.9 grams, was recrystallized from 2- propanol to give 2-nitrotrimethylene diethyldithiocarbamate melting at C.-91C. The structure was determined from infrared and nuclear magnetic resonance spectra and elemental analysis.

Analysis Calculated for C H N S O,: C, 41.11; H, 6.55; N, 10.95; S, 33.43. Found: C, 41.15; H, 7.04; N, 11.28; s, 33.68. 2-Nitrotrimethylene diethyldithiocarbamate was also obtained from the above reactants in dimethylformamide solution.

EXAMPLE 3 2-Nitrotrimethylene 1-Piperidinecarbodithioate Piperidiniurn l-piperidinecarbodithioate (49.2 grams, 0.20 mole), formaldehyde (16.2 grams of 37 aqueous solution, 0.20 mole), carbon disulfide (7.6 grams, 0.10 mole) and nitromethane (6.1 grams, 0.10 mole) were dissolved in methanol (200 ml.). A mildly exothermic reaction resulted, and after 2.5 hours, the reaction mixture was cooled to 1C. and the product was filtered off, washed with water, and dried in air. The crude product melted at 108.5C.120C. Repeated recrystallization from unheated methylene chloride-hexane solution gave Z-nitrotrimethylene 1- piperidinecarbodithioate melting at 128.5C.l33C. (prior sintering, gas evolution). The structure of the product was determined from infrared and nuclear magnetic resonance spectra and elemental analysis.

Analysis Calculated for C, H N S O C, 44.20; H, 6.18; N, 10.31; S, 31.46. Found: C, 44.31; H, 6.22; N, 10.24; S, 31.74.

EXAMPLE 4 2-Nitro-l-phenyltrimethylene Dimethyldithiocarbamate and Related Compounds A miirture of a-(nitromethyDbenzyl dimethyldithiocarbamate (8.1 grams, 0.030 mole), formaldehyde (2.4 grams of 37 percent aqueous solution, 0.030 mole), dimethylammonium dimethyldithiocarbamate (5.0 grams, 0.030 mole), and carbon disulfide (2.3 grams, 0.030 mole) in ml. of dimethylformamide was allowed to stand at 25C. No exotherm was apparent, but within 3 hours a solid began to precipitate. After 22 hours, the reaction mixture, a moist cake, was diluted with acetone (100 ml.) and the solid was filtered off. The white crude product, m.p. 142C.l46.5C. (gas evolution). weighed 10 grams (83 percent yield). Repeated recrystallization from methylene chloride-hexane solution without heat gave pure 2-nitro-l-phenyltrimethylene dimethyldithiocarbamate, melting at 145C.-15lC. (sinter 143C., gas evolution).

Analysis Calculated for C, H ,N S O C, 44.64; H, 5.25; N, 10.41; S, 31.78. Found: C, 44.99; H, 5.30; N, 10.45;S, 32.14.

Reaction of 3,4-dimethoxy-a-(nitromethyl)benzyl ethyldithiocarbanilate with formaldehyde and dimethylammonium dimethyldithiocarbamate in the presence of carbon disulfide yields 3,4-dimethoxy-a- (2-mercapto-1-nitroethy1)benzyl ethyldithiocarbanilate ester with dimethyldithiocarbamic acid.

Employing the above procedure but substituting a- (nitromethyl)benzyl ethylmethyldithiocarbamate for a-(nitromethyDbenzyl dimethyldithiocarbamate yields a-(Z-mercapto-l-nitroethyl)benzyl ethylmethyldithiocarbamate ester with dimethyldithiocarbamic acid.

Also using a-(nitromethylene)benzyl ethylmethyldithiocarbamate and ethylmethylammonium ethylmethyldithiocarbamate in the above reaction yields 2- nitro-l-phenyltrimethylene ethylmethyldithiocarbamate.

Also, using p-bromo-a-(nitromethyl)benzyl dimethyldithiocarbamate and dimethylammonium dimethyldithiocarbamate yields 2-nitro-1-(pbromophenyl)trimethylene dimethyldithiocarbamate.

EXAMPLE 5 2-Nitropropyl Dimethyldithiocarbamate and Related Compounds Nitroethane (7.5 grams, 0.10 mole) was added in one portion to a solution of formaldehyde (8.1 grams of 37 percent aqueous solution, 0.10 mole), carbon disulfide (7.6 grams, 0.10 mole), and dimethylammonium dimethyldithiocarbamate (16.6 grams, 0.10 mole) in 95 percent ethanol (50 ml.) and the resulting solution was kept at 23C. for 21 hours. The solution was then poured into water (850 ml.) and the precipitated oil was taken up in methylene chloride. The dried solution was concentrated in a rotary evaporator to leave an oil which was chromatographed on Florisil and silica gel to leave 6.5 grams of an amber oil which was crystallized from 30 ml. of cold methanol to give 5.7 grams of the product, melting at 37C42.5C. Repeated recrystallizations without heat from methanol and ethanol gave pure 2-nitropropyl dimethyldithiocarbamate melting at 38.5(.-4l(. The structure was proved by infrared and nuclear magnetic resonance spectra and ele mental analysis.

Analysis Calculated for C H N S O C, 34.59; H, 5.81; N, 13.45; S, 30.78. Found: C, 34.77; H, 5.92; N, 13.41; S, 30.54.

Substitution of di-n-butylammonium di-n-butyldithiocarbamate for dimethylammonium dimethyldithiocarbamate in the above reaction yields the 2- nitropropyl di-n-butyldithiocarbamate. Similarly, the 2- nitropropyl ethylmethyldithiocarbamate can be prepared using the ethylmethylammonium ehtylmethyldithiocarbamate. Moreover, when nitropropane is substituted in any of these reactions, the corresponding 2-nitrobutyl dialkyldithiocarbamate is formed.

EXAMPLE 6 2-Nitrobutyl Dimethyldithiocarbamate and Related Compounds Nitropropane (17.8 grams, 0.20 mole), forma1- dehyde (16.2 grams of 37 percent aqueous solution, 0.20 mole), carbon disulfide (15.2 grams, 0.20 mole), and dimethylammonium dimethyldithiocarbamate (33.2 grams, 0.20 mole) were dissolved in methanol ml.). A mildly exothermic reaction resulted. After 21.5 hours, the reaction mixture was poured into water (850 ml.) and the precipitated oil was washed with water and then taken up in methylene chloride. The dried solution was concentrated in a rotary evaporator to leave an amber oil. A small sample of the product was chromatographed on Florisil adsorbant giving an oil which solidified when chilled in methanol solution. The main sample crystallized from cold methanol solution when it was seeded. Repeated recrystallization from cold methanol gave pure 2-nitrobutyl dimethyldithiocarbamate melting at about 23C. The structure was determined from infrared and nuclear magnetic resonance spectra and elemental analysis.

Analysis Calculated for C H N O S C, 37.82; H, 6.35; N, 12.60; S, 28.84. Found: C, 37.99; H, 6.43; N, 12.66;S, 28.60.

Substituting diisopropylammonium diisopropyldithiocarbamate for dimethylammonium dimethyldithiocarbamate in the above reaction yields 2-nitrobutyl diisopropyldithiocarbamate.

EXAMPLE 7 3-Dimethylamino-2-methyl-2-nitropropyl Nitroethane (7.5 grams, 0.10 mole) was added to a Recrystallizations without heat from carbon tetrachloride-hexane solution gave pure 3- dimethylamino-2-methyl-2-nitropropyl dimethyl- EXAMPLE 8 1,3-Bis(2,4-dichlorophenyl)-3-dimethylamino-2- nitropropyl Dimethyldithiocarbamate and Related Compounds ClIaNOz A solution of dimethylammonium dimethyldithiocarbamate (16.6 grams, 0.10 mole), 2,4-dichlorobenzaldehyde (17.4 grams, 0.10 mole) and nitromethane (3.2 40

grams, 0.050 mole) in 95 percent ethanol (50 ml.) was allowed to stand at 23C. for 24 hours. The resulting precipitate was filtered off, washed with cold 95 percent ethanol, and dried in air. Recrystallization from acetone-ethanol solution (without heating) gave 1,3- bis(2,4-dichlorophenyl)- 3-dimethylamino-2- nitropropyl dimethyldithiocarbamate melting at 152C.154C.

methyldithiocarbamate for dimethylammonium dimethyldithiocarbamate in the above reaction yields l,3-bis-(2,4-dichlorophenyl)-3-ethylmethylamino-2- nitrophenyl ethylmethyldithiocarbamate.

EXAMPLE 9 2-(1-Hydroxyethylidene)-3-oxobuty1 Dimethyldithiocarbamate and Related Compounds -CSS'H N (CH Dimethylammonium dimethyldithiocarbamate (33.2 grams, 0.20 mole), formaldehyde (16.2 grams of 37 percent aqueous solution, 0.20 mole), 2,4-pentanedione (20.0 grams, 0.20 mole), and carbon disulfide (15.2 grams, 0.20 mole) were dissolved in methanol.(100 ml.). The temperature of the resulting reaction was kept below 27C. with ice cooling. After three hours at 22C.29C., the reaction mixture was 25 cooled in ice and the precipitated product was filtered off, washed with cold methanol and water, and dried in air. The crude product, melting at 69.5C.-71.C. (prior sintering) weighed 37.3 grams (80%). Repeated precipitation of the material from carbon tetrachloride solution by the addition of hexane gave pure 2-(1- hydroxyethylidene)-3-oxobutyl dimethyldithiocarbamate melting at 70C. -72C. The structure was determined from infrared and nuclear magnetic resonance spectra and elemental analysis.

Analysis Calculated for C H NS O E C, 46.32; H, 6.48; N, 6.00; S, 27.48. Found: C, 46.54; H, 6.43; N, 5.98; S, 27.08.

2-(l-Hydroxyethylidene)-3-oxobutyl ethylmethyldithiocarbamate is prepared by substituting ethylmethylammonium ethylmethyldithiocarbamate for dimethylammionium dimethyldithiocarbamate in the above reaction.

EXAMPLE l0 Acetylethylene Dimethyldithiocarbamate and Related The structure of the product was determined from infrared and nuclear magnetic resonance spectra and elemental analysis.

Analysis Calculated for C H N O S CM: C, 44.37; H, 3.91; N, 7.76; S, 11.86; C], 26.19. Found: C, 44.43; H, 3.78; N, 7.72; S, 11.78; Cl, 26.40.

Substituting benzaldehyde for 2,4-dichlorobenzaldehyde in the above reaction yields 1,3-diphenyl-3- dimethylamino-2-nitropropyl dimethyldithiocarbamate. Also substituting ethylmethylammonium ethyl- A solution of acetonyl dimethyldithiocarbamate (3.6 grams, 0.020 mole), formaldehyde (1.6 grams of 37 percent aqueous solution, 0.020 mole), carbon disulfide (0.010 mole, 0.8 gram), and dimethylammonium dimethyldithiocarbamate (3.3 grams, 0.02 mole) in methanol (15 ml.) was stirred and heated at 39C.- 43C. for 160 minutes. The reaction mixture was then cooled in ice and the precipitated product was filtered off, washed with cold methanol, and dried in air. The yield of product melting at l04C.-ll06.5C. (prior sintering) was 5.2 grams (84 percent). Repeated recrystallization from methylene chloride-methanol solution without heat gave the analytical sample of 1- acetylethylene dimethyldithiocarbamate melting at 105C.107.5C. (prior sintering). The structure was determined from the infrared spectrum and elemental analysis.

Analysis Calculated for C, ,H N S,O: C, 38.68; H, 5.84; N, 9.02; S, 41.30. Found: C, 38.92; H, 5.85; N, 9.19;S,42.30.

Acetylethylene diisopropyldithiocarbamate, acetylethylene di-n-butyldithiocarbamate and acetylethylene ethylpropyldithiocarbamate can all be made by the above procedure by substituting the corresponding acetonyl dialkyldithiocarbamate and dialkylammonium dialkyldithiocarbamate for acetonyl dimethyldithiocarbamate and dimethylammonium dimethyldithiocarbamate in the above reaction.

liXAMlLli ll Bcnzoylethylenc Dimethyldithiocarbamate A solution of phenacyl dimethyldithiocarbamate (12.0 grams, 0.050 mole), formaldehyde (4.1 grams of 37 percent aqueous solution, 0.050 mole), carbon disulfide (1.9 grams, 0.025 mole), and dimethylammonium dimethyldithiocarbamate (8.3 grams, 0.050 mole) in methanol (50 ml.) was stirred and heated at 38C.4()C. for 2.5 hours. The reaction mixture was then cooled to C. and the precipitated product was filtered off, washed with cold methanol and dried in air. The yield of product melting at 106C.l08.5C. was 17.6 grams (94 percent). Repeated recrystallization from methylene chloride-methanol and acetone-2- propanol solution without heat gave pure 1- benzoylethylene dimethyldithiocarbamate melting at 106C.l09.5C. The structure was determined from the infrared spectrum and elemental analysis.

Analysis Calculated for C H N S O: C, 48.35; H, 5.41; N, 7.52; S, 34.42. Found: C, 48.30; H, 5.37; N, 7.49; S, 34.65.

EXAMPLE 12 Rhodanine (13.3 grams, 0.10 mole) was added to a solution of dimethylammonium dimethyldithiocarbamate (16.6 grams, 0.10 mole), formaldehyde (8.1 grams of 37 percent aqueous solution, 0.10 mole), and carbon disulfide (3.8 grams, 0.050 mole) in methanol ml.). The temperature of the resulting exothermic reaction was held to 31C. with ice cooling. After the exothermic reaction was completed, the reaction mixture was stirred for 2.5 hours at 25C., and then the yellow product was filtered off, washed with methanol and dried in air. For further purification, the compound was slurried in carbon disulfide and in methanol to give the desired product, melting at 143C.145.5C. (gas evolution). The structure was determined from the infrared spectrum and elemental analysis.

Analysis Calculated for C ,H, N=,S,O: C, 37.12; H, 5.30; N, 12.99; S, 39.64. Found: C, 36.98; H, 5.22; N, 12.87; S, 39.84.

l'lXAMll .1. l3

a-(Nitromethyl)benzyl Dimcthyldithiocarbamutc CHzN Oz A solution of dimethylammonium dimethyldithiocarbamate (16.6 grams, 0.10 mole), carbon disulfide (7.6 grams, 0.10 mole), benzaldehyde (21.2 grams, 0.20 mole), and nitromethane (9.2 grams, 0.15 mole) in 95 percent ethanol (50 ml.) was allowed to stand at 23C. for several days. The resulting precipitate was filtered off, washed with cold 95 percent ethanol, and dried in air. The solid product, which melted at 101C.-102C., was recrystallized from 2-propanol to give a- (nitromethyl)benzyl dimethyldithiocarbamate melting at 105C.106C. The structure was determined from infrared and nuclear magnetic resonance spectra and elemental analysis.

Analysis Calculated for C H N S O C, 48.86; H, 5.21; N, 10.36; S, 23.71. Found: C, 49.31; H, 5.07; N,

EXAMPLE 14 Dimethyldithiocarbamic Acid S-Ester with 5- (Dimethylaminomethy)-5- (mercaptomethyl)rhodanine CHzNOz Dimethylammonium dimethyldithiocarbamate (16.6 grams, 0.10 mole), carbon disulfide (7.6 grams, 0.10 mole), and fl-nitrostyrene (14.9 grams, 0.10 mole) were dissolved in methanol (50 ml.). A rapid exothermic reaction ensued and the product precipitated. The reaction temperature was held to 35C. with ice cooling. After several hours at 25C., the product was filtered off, washed with methanol, and dried in air. The crude product melted at ca. 103C.-110C. and weighed 22.9 grams percent). Recrystallizations from hot methanol and from acetone-Z-propanol solu- Analysis Calculated for c u n s o C, 54.16; H, tion (without heating) gave 13.8 grams of a- 5.84; N, 9.03; S, 20.66. Found: C, 54.35; H, 5.80; N, (nitromethyl)-benzyl dimethyldithiocarbamate melting 8.87; S, 2089.

at 104C.l08.5C. (prior sintering). The infrared spectrum was essentially identical to the spectrum of EXAMPLE 17 analytically pure material. 2,4-Dichloro-a-(nitromethyl)benzyl When the reaction was repeated with the same pro- Dimethyldithiocarbamate l o1- o11o1mo (UlIn)2N(lHS llzN ((ll1:12 (1S3 1 (CHrlzN-GSSTII-CI CHzNOz portions except that the carbon disulfide was omitted, 2,4-Dichloro-B-nitrostyrene (6.6 grams, 0.030 mole) the pr ip co ed of bou 0 p ent o was added to a stirred solution of dimethylammonium yn y dimethyldithiocal'bamate and dimethyldithiocarbamate (5.1 grams, 0.030 mole) and about 80 Percent of a resinous -p carbon disulfide (1.8 ml., 0.030 mole) in methanol 30 EXAMPLE 15 ml.). The temperature of the resulting reaction was l632C. After 2 hours at room temperature, the a-(NitromethyDbenzyl l-Pyrrolidinecarbodithioate precipitated product was filtered off, washed with cold BNkmstwene (7 5 grams 0 050 mole) was added to methanol, and dried in air. Recrystallization without a cooled (moa) Stirred Slurry of ammonium heating was accomplished by dissolving the sample in rolidinecarbodithioate (32 grams, 0050 mole) in acetone and then adding absolute ethanol to give 2,4- methanol (50 ml.). The temperature of the mixture fell 'l y l' y dlmethyldlthlocarba' to 5C., then rapidly climbed to 10C. The cooling bath mate melting at 12700-12800 was removed and the reaction temperature rose slowly Analysis Calculated u iz z z z z C, to 22C. Acetic acid 3.0 grams, 0.05 mole) was added, 1 2 Found: the slurry was cooled to 10C. and the solid was filtered H, 1832;

off, washed with water, and dried in air. The crude product melted at lO8C.-116C. and weighed 11.4 EXAMPLE18 grams (77 percent yield) Repeated recrystallizations 3 from cool acetone-methanol, hot acetone-2-propanol, and cool methylene chloride-toluene-hexane solutions al-Nitroethyl)benzyl Dimethyldithiocarbamate (CH1)zNCSS HzN (CH3) gave pure a-(nitromethyDbenzyl l-pyrrolidinecar- (3H3 llaogitchipate melting at ll6C.-120C. (sintering at 40 C32 *7 Analysis Calculated for C H N S- O C, 52.68; H, CHaAIDHNO2 5.44; N, 9.45; s, 21.63. Found: c, 53.01; H, 5.28; N, CH3 NCS S'CH As in Example 17, reaction of (2-nitro'2-prope- EXAMPLE 16 5 ny])benzene with dimethylammonium dimethyldithiocarbamate in the presence of carbon disulfide, a-(Nitromethyl)benzyl l-Piperidinecarbodithioate gave a-(1-nitroethyl)benzyl dimethyldithiocarbamate B-Nitrostyrene 14.9 grams, 0.10 mole) was added in melting at 92C. 94C. when recrystallized without portions to a stirred mixture of piperidinium lheating from acetone-ethanol solution. piperidinecarbodithioate (24.6 grams, 0.10 mole), and Analysis Calculated for c u n s o C, 50.67; H, carbon disulfide (7.6 grams, 0.10 mole) in methanol 5.67; N, 9.85; S, 22.55. Found: C, 50.93; H, 5.71; N, (200 ml.). During the addition, the reaction tempera- 9.79; S, 22.80. ture was 25C.29C. After the addition of 5- nitrostyrenc, the reaction mixture was cooled to 8C., EXAMPLE :v ii h v s gtsr fziiii gi 'i sd 1: 2:: 'l'll Siil di ir uzi iiis a-( Nitromethyl )benzyl Dicthyldithiocarbamutc ing at 85C.-87C. (prior sintering) was 29.0 grams (93 5 (011102144:s s n2N (c2n, z percent). Repeated recrystallizations without heating from methylene chloride-hexane and methylene CH=UHNOZ chloride-methanol solutions gave pure a- (nitromethyl)benzyl 1-piperidinecarbodithioate melting at 86C.-90.5C. (prior sintering).

As in Example 17, reaction of B-nitrostyrene with diethylammonium diethyldithiocarbamate in the presence of carbon disulfide gave a- (nitromethyl)benzyl diethyldithiocarbamate melting at 81C.82.5C. When recrystallized without heating from acetone-Z-propanol solution.

Analysis Calculated for C H N S O C, 52.32; H, 6.08; N, 9.39; S, 21.49. Found: C, 51.79; H, 6.04; N, 9.24;S, 21.03.

EXAMPLE 20 a, a'-Bis(nitromethyl)-p-phenylenedimethylene Dimethyldithiocarbamate 2 (prismo s s 9111N(CH3)1 As in Example 17, reaction of one mole of 1,4 -bis(2- nitrovinyl)benzene with two moles of dimethylammonium dimethyldithiocarbamate in the presence of carbon disulfide gave a,a-bis(nitromethyl)-p-phenylenedimethylene dimethyldithiocarbamate, which did not have a definite melting point.

Analysis Calculated for C H N S O C, 41.53; H, 4.79; N, 12.11; S, 27.72. Found: C, 41.64; H, 5.06; N, 12.10; S, 27.54.

EXAMPLE 21 2-Acetoxy-3-methoxy-a-(nitromethyl)benzyl Dimethyldithiocarbamate cmmwc s s nm wum l l CH3COO OCH;

As in Example 17 reaction of 2-methoxy-6-(2- nitrovinyl)phenyl acetate from Example 22 with dimethylammonium dimethyldithiocarbamate in the presence of carbon disulfide gave 2-acetoxy-3-methox- 5.06; N, 7.82; S, 17.89. Found: C, 46.74; H, 5.19; N, 7.7l;S,17.89.

EXAMPLE 22 2-Methoxy-6-( 2-nitrovinyl)phenyl Acetate 1 CHJO OH CHaA) (BCOCH;

EXAMPLE 23 2-Chloro-5-nitro-a-( nitromethyl )benzyl Dimethyldithiocarbamate (Ill CHzNOz NO;

As in Example 17, reaction of 2-chloro-B5- dinitrostyrene with dimethylammonium dimethyldithiocarbamate in the presence of carbon disulfide gave 2-chloro-5-nitro-a-(nitromethyl)-benzyl dimethyldithiocarbamate melting at 120C.-121C. after recrystallization without heating from acetonemethanol solution.

Analysis Calculated for C, H,,N S O,Cl: C, 37.77; H, 3,46; N, 12.01;S, 18.33; Cl, 10.13. Found: C, 37.81; H, 3.44;N, 12.01;S, 18.39;Cl, 10.11.

EXAMPLE 24 4-Acetoxy-a-(nitromethyl)benzyl Dimethyldithiocarbamate y-a-(nitromethyl)benzyl dimethyldithiocarbamate melting at 124C.-125.5C. after recrystallization without heating from dimethylformamide-methanol solution.

Analysis Calculated for C H N S O C, 46.91; H,

CH1NO:

As in Example 17, reaction of 4-acetoxy-B- nitrostyrene with dimethylammonium dimethyldithiocarbamate in the presence of carbon disulfide gave 4-acetoxy-a-(nitromethyl)benzyl dimethyldithiocarbamate melting at 116C.-118C. after recrystallization without heating from acetone- As in Example 17, reaction of o-chloro-B- methanol solution. nitrostyrene with dimethylammonium dimethyl- Analysis Calculated for C t-1 N5 C, 47.55; H, dithiocarbamate in the presence of carbon disulfide 4.91; N, 8.53; S, 19.53. Found: C, 47.52; H, 4.80; N gave o-chloro-a-(nitromethyl)benzyl dimcthyl- 8.3S;S, 19.58. 5 dithiocarbamate melting at 102C.103.5C. when recrystallized without heating from acetone-methanol EXAMPLE 25 solution.

3,4-Dimethoxy-a-(nitromethyl)benzyl Analysis Calculated for c,,H,,N s,o,c1= C, 43.34; Dimethyldithiocarbamate H, 4.30; N, 9.19; S, 21.04. Found: C, 43.17; H, 4.02; N,

| CH; O

CH2NO2 l QCHa As in Example 17, reaction of 3,4-dimethoxy-B- 9.22;S,21.l4. nitrostyrene with dimethylammonium dimethyldithiocarbamate in the presence of carbon disulfide EXAMPLE 28 gave 3,4-dimethoxy-a-(nitromethyl)-benzyl dimethyldithiocarbamate melting at l08C.ll0C. after recrystallization without heating from acetonemethanol solution.

Analysis Calculated for C H N S O C, 47.26; H, 6 5.49;N, 8.48;S, 19.41. Found: c, 47.19;!1, 5.50; N,

3 ,4-( Methylenedioxy )a-( Nitromethyl )benzyl Dimethyldithiocarbamate EXAMPLE 26 p-Isopropyl-a-(nitromethyl)benzyl CHZN 02 Dimethyldithiocarbamate Q (CHs)zNCS-SCH -o ommwo SS HzN (CHa)z (CH;)zCH- -CH=GHNO2 as? As in Example 17, reaction of 3,4-(methylenedioxy)- CH2NO2 40 B-nitrostyrene with dimethylammonium dimethyldithiocarbamate in the presence of carbon disulfide (CHmM-CSS CH CH(CH9 gave 3,4-(methylenedioxy)-a-(nitromethyl)benzyl dimethyldithiocarbamate melting at l22C.-l24C.

AS in Example 17 reaction f q pg when recrystallized without heating from acetonenitrostyrene with dimethylammonium dimethylethanol 9 dithiocarbamate in the presence of carbon disulfide Analysls Calculated for 12 14 2 2 4 C, 4535;

gave p isopropyl a (nitromethyl)benzy] dimethy]- 4.49; N, 8.91; S, 2040. Found: C, 46.06; H, 4.53; N, dithiocarbamate melting at ll9C.-120C. after 8973,2051- recrystallization without heating from acetone- EXAMPLE 29 methanol solution.

Analysis Calculated for C H N S O C, 53.82; H, p.MethoXy a (nitromethynbenzyl 6.45; N, 8.97; S, 20.52. Found: C, 53.74; H, 6.28; N, Dimethyldithiocarbamate 8.99;S, 20.46.

CHzNOz EXAMPLE 27 (CH3);NC S-S-CH-0GH3 o-Chloro-a-(nitromethyl)benzyl Dimethyldithiocarbomate As in Example 17, reaction of p-methoxy-B- z (CH3): nitrostyrene with dimethylammonium dimethyldithiocarbamate in the presence of carbon disulfide gave p-methoxy-a-(nitromethyl)benzyl dimethyl- CH:CHNO2+ CS dithiocarbamate melting at 86C.89C. when recrystallized without heating from acetone-ethan0l 5 solution. CH,,,N- Analysis Calculated for c n ms o c, 47.98; H, I 5.37; N, 9.32; S, 21.35. Found: C, 48.19; H, 5.44; N,

Cl 9.25;S,21.21.

C HiN Oz EXAMPLE 30 p-Bromo-a-(nitromethyl )benzyl Dimethyldithiocarbamate CHzNO;

(CH3)2NCSS( JH-Br As in Example 17, reaction of p-bromo-B- nitrostyrene with dimethylammonium dimethyldithiocarbamate in the presence of carbon disulfide gave p-bromo-a-(nitromethyl)benzyl dimethyldithiocarbamate melting at 79C.-81C. when recrystallized without heating from acetone-ethanol solution.

Analysis Calculated for C H N S O Br: C, 37.82; H, 3.75; N, 8.02; S, 18.36; Br, 22.88. Found C, 37.73; H, 3.80; N, 8.05; S, 18.21; Br, 22.93.

EXAMPLE 31 l-N aphthyl-Z-nitroethyl Dimethyldithiocarbamate CHzNOz As in Example 17, reaction of 1-(2-nitrovinyl)naphthalene with dimethylammonium dimethyldithiocarbamate in the presence of carbon disulfide gave 1-naphthy1-2-nitroethyl dimethyldithiocarbamate melting at 136C.138C. when recrystallized without heating from dimethylformamide-methanol solution.

Analysis Calculated for C, H N S O C, 56.23; H, 5.03; N, 8.74; S, 20.01. Found: C, 56.29; H, 5.05; N, 9.00; S, 20.15.

EXAMPLE 32 a-(Nitromethy1)furfuryl Dimethyldithiocarbamate As in Example 17, reaction of 2-(2-nitrovinyl)furan with dimethylammonium dimethyldithiocarbamate in the presence of carbon disulfide gave a- (nitromethyl)furfury1 dimethyldithiocarbamate melting at 67C.-68C. after recrystallization from methanol.

Analysis Calculated for C,H, N S O C, 41.52; H, 4.65; N, 10.76; S, 24.63. Found: C, 41.61; H, 4.54; N, 10.79; S, 24.71.

EXAMPLE 33 a-(Nitrom ethyl)-2-thenyl Dimethyldithiocarbam ate ClIzNOz EXAMPLE 34 5-Chloro-a-(nitromethyl )-2-thenyl Dimethyldithiocarbamate S Cl CH=CH-NO2 CHzNOz As in Example 17, reaction of 2-chloro-5-(2-nitrovinyl)thiophene with dimethylammonium dimethyldithiocarbamate in the presence of carbon disulfide gave 5-chloro-a-(nitromethyl)-2-thenyl dimethyldithiocarbamate melting at 76C.77C., after recrystallization without heating from acetonemethanol solution.

Analysis Calculated for C H N S O CI: C, 34.77; H, 3.57; N, 9.01; S, 30.95; Cl, 11.41. Found: C, 34.95; H, 3.62;N, 9.05;S, 30.99;C1, 11.31.

EXAMPLE 35 a-(Nitromethyl)benzyl N-Methyldithiocarbanilate and a Related Compound CHZNOQ CH;

Ammonium N-methyldithiocarbanilate (15.0 grams,

0.075 mole) is added in 4 equal portions to a solution of B-nitrostyrene (11.2 grams, 0.075 mole) in 100 ml. of methanol. After each addition of ammonium N- methyldithiocarbanilate, acetic acid (1.1 grams, 0.019 mole) is added. The reaction temperature is maintained at 7C.-10C. during the additions, then the reaction mixture is allowed to warm to 31C. and the crude yellow product, melting point 102C.-110C. (viscous melt), weight 12.5 grams, is filtered off. Recrystallizations without heat from methylene chloride-methanol give 5.0 grams of the off-white product, melting point 1 10.5C.-1 14C. For further purification, the product is recrystallized without heat from aqueous acetone, acetone and methylene chloride-methanol, consecutively, giving pure a- (nitromethyl)benzyl N-methyldithiocarbanilate, melting point 111C.1l6C., as shown by infrared and nuclear magnetic resonance spectra and elemental analysis.

Analysis Calculated for C H N S O C, 57.81; H, 4.85; N, 8.43; S, 19.29. Found: C, 57.59; H, 4.83; N, 8.32;S, 19.69.

Reaction of 3,4-dimethoxy-B-nitrostyrene with ammonium ethyldithiocarbanilate by the above procedure yields 3,4-dimethoxy-a-(nitromethyl)benzyl ethyldithiocarbanilate.

EXAMPLE 37 Spore Germination The activity of the compounds of the invention for controlling pathogenic organisms responsible for diseases in agricultural crops is further demonstrated by the following tests employing the organisms Monilinia fructicola, the pathogen responsible for American brown rot in stone fruits; Stemphylium sarcinaeforme, the pathogen which incites leaf spot in legumes; and Aspergillus niger, the saprophyte responsible for degradation of textiles, fabrics, leather, and vegetables.

The test procedure involves the preparation of a 100, 10 or 1 ppm. suspension of test compound in water. The solutions are placed in one dram opticlear vials and separately inoculated with one drop of a spore suspension prepared from 7-day cultures of Aspergillus niger and 14-day old cultures of Monilinia fructicola and Stemphylium sarcinaeforme, all grown on potatodextrose agar. The vials containing the separately inoculated solutions of test compounds are then capped and placed on a rotating tumbler for 24 hours to assure contact of the organism with the test compound. After 24 hours, the vials are removed and examined for inhibition of growth of mycelium.

The data obtained from the title compounds of the indicated examples are presented in Table 1 below.

TABLE I Percent inhibition of spore germination Mom'linia Stemphylium Asperqillus fructicola sarcinaeforme m'yer Concentration (p.p.m.) 100 10 1 100 10 1 100 10 1 Compound of Example:

1 100 100 100 100 100 100 100 100 100 100 0 0 100 100 0 100 100 100 100 100 100 100 100 100 100 100 100 0 100 100 0 100 0 100 100 0 100 0 (l 100 NM) 100 0 0 100 100 100 100 100 100 100 100 100 100 (l 100 0 100 100 100 100 100 (I 1011 0 100 100 100 100 100 (l (l l) 100 (l 0 100 0 0 100 100 100 100 100 100 100 0 0 0 100 0 0 100 0 0 EXA M PLE 3 8 EXAMPLE 36 a-(NitromethyDbenzyl Dimethyldithiocarbamate B-Nitrostyrene (14.9 grams, 0.10 mole) is added in portions to a stirred solution of dimethylammonium dimethyldithiocarbamate (8.3 grams, 0.05 mole) and carbon disulfide (3.8 grams, 0.05 mole). The temperature is maintained at 16C.26C. during the addition; then the reaction mixture is cooled to 5C. and the precipitate of a-(nitromethyUbenzyl dimethyldithiocarbamate is filtered off, washed with cold methanol and water, and dried in air. The yield of product, melting point 102C.-108C. (sinter 100C), is 25.3 grams (94 percent).

Similarly, gradual addition of dimethylamine (45.1 grams, 1 mole) to a methanol solution of carbon disulfide (83.6 grams, 1.1 mole) and B-nitrostyrene (149.1 grams, 1 mole) at 10C.30C. yields (nitromethyl)benzyl dimethyldithiocarbamate.

Antibacterial Activity Test compounds are added to separate test tubes of deionized sterile water at the rate of ppm. final concentration. Separate treated tubes are inoculated with one drop of 24-hour broth cultures of Aerobacter aerogenes, Staphylococcus aureus, or Xanthomonas vesicatoria. The tubes are incubated for 24 hours at room temperature. At the end of 24 hours, 1.1 ml. of sterile peptone broth is added to tubes aseptically, and the tubes are incubated at 37C. for 24 hours. At the end of 24 hours, all tubes are clear so subcultures are made to new untreated tubes and these incubated for 72 hours at 37C. At the end of this period, all tubes are examined and rated.

0 No Effect 9 Kill of Bacteria 5 Stasis, but not Kill of all Bacteria The data obtained for the title compounds of the indicated examples are presented in Table 11 below.

TABLE II Antibacterial Activity Aerabacter Staphylococcus Xanlhomonas Compound aerogener aureus vesicaloria of Concentration (ppm.) Example 100 100 100 l 0 7 9 9 5 13 5 5 5 8 0 5 0 l7 0 5 0 30 0 5 0 28 9 5 5 33 0 5 0 18 0 5 0 27 9 5 5 26 0 5 0 25 5 5 5 9 0 5 0 6 9 9 9 10 99 S l 1 0 5 0 EXAM PLE 39 Test compounds were incorporated in a Sabouraud's dextrose agar in an amount sufficient to provide the active ingredient in a concentration of about 100 ppm. A 20-ml. sample of the agar mixture is placed in a petri dish and permitted to solidify. An agar sample is inoculated with the test organism set forth below and then covered and incubated for a period of about 72 hours at 23C. After incubation, growth observations are made. The test results are recorded and the test is repeated twice for the purpose of comparison.

The data obtained with a variety of test organisms is shown in the table below, and ratings are shown as 0 or 5. 0 indicates no control, 5 indicates 100 percent effectiveness of the test compound against the specified organism.

Abbreviations are as follows:

An Aspergillus niger Fl Fusarium lycopersici Mf= Monilinia fructicola Pd Pythium de Baryanum Rs Rhizoctom'a solani S5 Slemphylium .varcinaeforme Ps Pseudomonas .rolaracaerum C1 Collectotrichum lagenarium Va Verticillium alba-atrum The data obtained for the title compounds of the indicated examples are presented in Table [11 below.

TABLE III 100 p.p.m. agar dilution plate Compound 01 Example Au Fl M1 Pd Rs SS ls (fl \'u 0 0 5 0 0 5 0 5 1) 0 0 0 0 0 ll 0 5 l) 0 O 5 U 5 5 0 5 5 U 5 5 5 0 5 (l 5 5 O 0 5 0 0 0 (l 0 5 0 0 0 0 0 0 0 5 5 0 0 5 5 5 0 0 5 0 0 0 5 5 0 5 0 5 5 0 0 5 0 0 5 0 5 0 0 5 5 5 5 5 0 5 5 0 0 5 0 0 0 0 0 0 0 5 5 5 0 5 O 5 5 0 0 5 5 5 5 0 5 5 0 0 5 5 0 5 0 5 5 0 0 O O 0 0 0 5 0 5 5 5 5 5 5 0 5 5 0 0 5 5 5 5 0 5 5 0 0 5 0 0 5 0 5 5 0 0 O 0 5 0 0 5 0 5 5 5 5 5 5 0 5 5 0 0 5 0 0 0 0 5 0 28 EXAMPLE 40 Apple Scab (Venturia inaequalis) on Field-Grown Trees The compound of Example 13 was applied as a foliar spray for 10 applications at weekly intervals from May 1 through July 2, and then two more sprays on a 2-week schedule ending on July 31.

The active compound was applied as a 50 percent wettable powder having the following composition:

50% Active Compound (Example 13) 1% Aerosol OS 2% Cellosize QP 15,000 4% Blancol N 43% Kaolinite 41 Rates of 50% wettable applied were:

2 pounds/ gallons of water 1 pound/100 gallons of water Three tree replicates of each rate Variety: Red Delicious were used.

Trees at the 2-pound rate remained free of scab all season long. The l-pound rate showed a trace of scab at the end of the season. No phytotoxicity was observed.

EXAMPLE 41 Field-Grown Tomatoes and Cantaloupes All compounds were applied at 4.8 pounds/100 gallons and 2.4 pounds/100 gallons of water per acre.

The tomato varieties used were Rutgers and Manalucie. These were treated eight times at weekly intervals. No phytotoxicity was noted with dry compound at any rate. Too little disease developed to rate for disease control.

The same compounds and rates were applied to cantaloupe for five weekly sprays. No phytotoxicity with dry compound, and too little disease to rate for disease control.

Formulations used were prepared as follows:

50% Wettable Powder Compound Example 1 50% Test Compound (Example 1) 1.1% Aerosol OS 3.5% Marasperse CB 45.4% Kaolinite 41 50% Wettable Powder Test Compound Example 18 50% Test Compound (Example 18) 10% Aerosol OS 3.5% Marasperse CB 45.5% Kaolinite 41 50% Wettable Powder Test Compound Example 13 50% Test Compound (Example 13) 1% Aerosol OS 2% Cellosize QP 15,000 4% Blancol N 43% Kaolinite 41 EXAMPLE 42 Solutions of various concentrations of test compounds are prepared in a mixture of equal parts by weight of acetone and water. The foliage of Bonny Best tomato plants with four true leaves, Early Marketeer cucumber plants with two true leaves, Nato variety rice plants and Red Delicious apple seedlings with eight to 14 true leaves were sprayed to run-off with the test solutions. The plants were allowed to dry and were then sprayed with a mixed inoculum of cucumber anthracnose (Colletotrichum lagenarium), tomato late blight (Phytophthora infestans), rice blast (Piricularia oryzae), and apple scab (Venturia inaequalis). The sprayed plants were held for 5 days in an incubation room under a water-saturated atmosphere at 18C., after which time the plants were removed and lesion counts were made. The results obtained, expressed in terms of the disease control index for the title compounds of the indicated examples are presented in the tables below.

TABLE IV Cucumber Anthracnose (Colletotrichum lagenarium) 5 clean, no disease 4 trace of disease 3 slight disease 2 moderate disease severe disease like controls N.T. no test TABLE V Tomato Late Blight (Phytophlhora infestans) Compound Dosage in ppm.

Example Number 1200 600 300 150 8 NT N.T. 5 at 500 5 at 100 17 5 5 4 28 N.T. N.T. 5 at 500 5 at 100 20 5 4 3 3 33 N.T. N.T. 5 5

l8 N.T. N.T. 5 at 500 5 at 100 32 5 5 4 4 31 N.T. NT. 5 at 500 5 at 100 24 N.T. N.T. 5 at 500 3 at 100 34 N.T. NT. 3 at 500 N.T.

23 N.T. N.T. 5 at 500 5 at 100 21 N.T. N.T. 5 at 500 N.T.

l0 N.T. N.T. 5 at 500 4 at I00 11 N.T. N.T. 4 at 500 3 at 100 I2 N.T. N.T. 5 5

3 N.T. N.T. 4 4

TABLE VI Rice Blast (Piricularia Oryzae) Compound Dosage in ppmv Example Number 1200 600 300 I50 l3 5 5 5 5 8 N.T N.T 5 at 500 5 at 100 I7 5 5 5 3 3O 5 5 5 5 29 5 5 5 4 28 5 5 0 O 33 N.T. N.T. 5 5 18 N.T. N.T. 5 at 500 5 at 100 32 5 5 0 0 19 5 5 3 3 27 4 4 4 2 26 5 5 4 4 25 4 5 4 3 9 4 3 2 0 31 N.T. N.T. 5 at 500 4 at 24 N.T. N.T. 4 at 500 3 at 75 34 NT N.T. 3 at 500 l at 75 23 N.T. N.T. 4 at 500 3 at 75 21 NT. N.T. 4 at 500 3 at 75 10 N.T. NT. 5 at 500 4 at 75 ll N.T. N.T. 4 at 500 3 at 75 12 N.T. N.T. 5 N.T. l5 N.T. NT. 4 4 3 N.T. N.T. 5 5 l6 N.T. N.Tr 5 5 TABLE VII Apple Scab (Venturia inaequalis) Compound Dosage in ppm. Example Number 1200 600 300 150 l 3 3 3 0 2 5 5 5 5 7 5 0 O 0 l3 5 5 5 5 8 5 5 5 4 17 5 5 5 0 30 5 5 5 5 29 5 5 5 5 28 5 5 0 O 33 5 5 5 5 l8 N.T. N.T. 5 at 500 5 at 32 5 5 0 0 l9 5 5 0 0 27 5 0 0 O 26 5 0 0 0 25 5 5 5 5 31 N.T. N.T. 4 at 500 N.T. 24 N.T. N.T. 5 at 500 N.T. 23 N.T. N.T. 4 at 500 N.T. 21 N.T. NT. 4 at 500 N.T. ll N.T. N.T. 5 at 500 N.T. l2 N.T. N.T. 5 5 16 N.T. N.T. 5 5

We claim: 1. A compound having the formula:

N-C S-SCHZ 2 R H-N0z wherein R, and R are each loweralkyl C -C.,; R is hydrogen or loweralkyl C -C and Z is phenyl, 1- naphthyl, or substituted phenyl said substituents being selected from the group consisting of chloro, bromo, lower alkyl, lower alkoxy, acetoxy and nitro.

2. A compound according to claim 1 having the formula:

NCS-SCH-- CH3 NO2 lI'l 3. A compound according to claim 1 having the formula:

CHsCIINO2 4. A compound according to claim 1 having the formula:

OCH;

5. A compound according to claim 1 having the formula:

6. A compound according to claim 1 having the formula:

CHr-NO; (CHs)2NCSS(| JH 7. A process for the preparation of a compound of the formula:

wherein R and R are each loweralkyl C -C R is hydrogen or loweralkyl C -C and Z is phenyl; comprising treating about one mole equivalent of a compound of the formula:

N-os-s m i R1 ITTO:

N-CS-S-CHr-CH-Ra where R and R are each loweralkyl C,-C and R is loweralkyl C -C comprising reacting approximately equimolar amounts of a compound of the formula:

formaldehyde and carbon disulfide in an aqueous lower alcohol solution with an equimolar amount of a 1- nitroalkane at about 20C. to 50C. 

2. A compound according to claim 1 having the formula:
 3. A compound according to claim 1 having the formula:
 4. A compound according to claim 1 having the formula:
 5. A compound according to claim 1 having the formula:
 6. A compound according to claim 1 having the formula:
 7. A process for the preparation of a compound of the formula:
 8. A process for the preparation of a compound of the formula: 